Toilet bars

ABSTRACT

TOILET BARS HAVING IMPROVED AFTER-WASH FEEL PROPERTIES COMPRISE AT LEAST 15% BY WEIGHT OF POLYETHYLENEOXIDE QUATERNARY AMMONIUM COMPOUNDS. THE LATTER MUST HAVE AT LEAST THREE ETHYLENEOXIDE UNITS IN A CHIAN AND SATISFY AN EXPRESSION RELATING THE NUMBER OF ETHYLENEOXIDE UNITS TO THE NUMBER OF CARBON ATOMS AND THE NUMBER OF QUATERNARY NITROGEN ATOMS.

United States Patent 3,838,057 TOILET BARS Andrew Nicholas MorrisonBarnes, Wallington, Wai

Ming Ghen, Ellesmere Port, Tudor Rickards, Upton, David Arthur Rosser,Wirral, and Ponnuswamy Thu a mian, Port. unligh E g and, gno to LeverBrothers Company, New York, N.Y.

No Drawing. Continuation of application Ser. No. 60,781,

July 30, 1970, which is. a continuation-in-partof application Ser. No.835,739, June 23, 1969, both now abandoned. This application July 3,1972, Ser. No. .68,,396;

Claims priority, application Great Britain, June 25, 1968,

30,255/68; July 12, 1968, 33,361/ 68 Int. Cl. C11d 9/30 U.S. Cl. 252-11725 Claims ABSTRACT OF THE DISCLOSURE Toilet bars. having improvedafter-wash feel properties comprise at least 15% by weight ofpolyethyleneoxide quaternary ammonium compounds. The latter must have atleast three ethyleneoxide units in a chain and satisfy an expressionrelating the number of ethyleneoxide units to thenumber of carbon atomsand the number of quaternary nitrogen atoms.

mainly based, on soaps but in recent years there has been an inereasinginterest in the use of other detergents.

Despite these advances the search for improvements for toilet, barsstill continues. In particular it has long been recognised that there isa conflict between the detergent and he cosmetic action of toilet bars.For instance, after washing with a toilet bar the skin often feelstie-oiled. Skin with this after-wash ,feel is often described as dry. Itis an object of the present invention to mitigate this after-wash feeland related eiiects at reasonable cost.

According to the present invention it has surprisingly been found thatif a toilet bar contains at least 15% by weight of a polyethyleneoxidequaternary ammonium compounds with certain characteristics givenhereafter, afterwash feel and related ei fects are improved; the skinfeels more pleasant and smoother. The characteristics required of thepolyethyleneoxide quaternary ammonium compounds used in the toilet barsof the present invention are that they must contain a polyethyleneoxidegroup containing at least three ethyleneoxide units in a straight chain(i.e. -CH .CH .O.CH .CH .O-.CH .CH .O.) The term polyethylenefoxidequaternary ammonium compounds used hereinafter refers to compounds withsuch polyethylene oxide groups.

Bars containing quaternary ammonium compounds have been disclosedearlier, for instance in UK patent specifications Nos. 443,795, 737,898and 759,837.Also a bar containing a minor amount of a quaternaryammonium compound containing a polyethyleneoxide group is disclosed inUK patent specification No. 1,027,898. But the surprising mpro d f tte-w sh eel and rela ed fi ts btained by. bars according to th Presentinvention, are neither disclosed nor envisaged.

The p eferred p ly hy en xid q a ry ammonium compounds have a K value offrom 3 to 0.01 when the 3,838,057 Patented Sept. 24, 1974 compound isdetersive and from 30 to 0:67'when the, compound is non-detersive, theKvalue being defined by the expression;

2 C X 2 f1 where 2(EO) is the total number of ethyleneoxide units, 20 isthe total number of carbon atoms not in ethyleneoxide units and is thetotal number of quaternary nitrogen atoms per repeating unit of thecompound. Most polyethyleneoxide compounds do not have repeating units,in which case the values of i 2030.), EC and 231 1.

pp to he mp und s. a hole. t; e a n p l hrb eneoxide compounds arepolymeric or may be regarded as dimers, in whichcase the values of 2 E020 and 281 pound having the formula alalasnn r-x for use in a baraccording to the invention the nature of the groups R R R and R, canvary very widely. But R R R or R may not behydrogen atoms since suchcompounds are better classified as salts of ternary ammonium compoundsrather than as quaternary ammonium compounds. Compounds are alsoexcluded in which any of the groups R R R and R contains an anionicgroup. Such compounds are better described as betaines than asquaternary ammonium compounds since the anionic group destroys theirquaternary nature. The groups R R R and R, can be straight-chain,branched-chain or cyclic alkyl; aryl; alkaryl; aralkyl; or heterocyclicgroups, and amongst the many substituent groups or linkages that can bepresent are ethylenic and acetylenic linkages, conjugated or otherwise,carbonyl, ester and amide groups and linkages, and halogen and nitrogroups. Also two or more of the groups R R R and R, can form aheterocyclic ring with the quaternary nitrogen atom. At least one of thegroups, R R R and R must comprise a polyethyleneoxide group containingat least three ethyleneoxide units, which may but need not be directlyattached to the quaternary nitrogen atom.

It will be appreciated that one or more of the groups R R R and R mayalso be linked to one or more further quaternary nitrogen atoms, eachwith its own substituent groups R R R and. R

For convenience, the term compatible qua ternary nitrogen substituentgroup is used hereinafter to cover all the types of group R R R and R;which can satisfactorily be used, as describedabove,

Any compatible anion X can be used with the quaternary ammoniumcompound. Preferred anions are mono valent, particularly the halides,i.e. chloride, bromide and iodide, but other anions which can be used.include, for example, sulphate, phosphate and acetate anions.

The necessary range for the K value as defined herein- 4 before dependson whether the polyethyleneoxide quaternary ammonium compound isdetersive or not. In general, it has been found that if apolyethyleneoxide quaternary ammonium compound contains a straight-chainof more than six carbon atoms, or an aralkyl or alkaryl group containingmore than eight carbon atoms, the polyethyleneoxide quaternary ammoniumcompound is detersive. Thus, for example, polyethyleneoxide quaternaryammonium compounds of the general formula:

where a+b+c is 9 or 27 and R is benzyl or ethyl are nondetersive.

The term E is used herein to designate the group CH .CH .O or, whenterminal, the group When the term is preceded by a number with a barabove, e.g. 1 1, this means that the product concerned contains onaverage the number of E0 groups indicated, that is fourteen in theexample. This terminology is used since polyethyleneoxide products areusually made by condensation of a compound containing a reactivehydrogen atom with ethyleneoxide, eg in the case of an alcohol thereaction is:

non 14 cH,cn, non E0 The product obtained is inevitably a mixture,containing, for example, some R.O.l2 EO and some R0. 16 E0 but onaverage it contains fourteen E0 units.

Whilst a polyethyleneoxide quaternary ammonium compound for use in a baraccording to the invention must, as specified above, contain at leastone group with 3 E0 units, it has been found that the preferredpolyethyleneoxide quaternary ammonium compounds contain at least one 5EO group.

The extent to which a bar according to the invention displays improvedafter-wash feel is particularly surprising when considering the extentof the effect with toilet bars containing a quaternary ammonium compoundnot containing a polyethyleneoxide group.

Presence in a quaternary ammonium compound of a polyethylene-oxide groupincreases water-solubility and would be expected to reduce any skineffect, see for instance B. Idson, J. Soc. Cosmetic Chemists, 1967, 18,91, particularly at page 99, last paragraph. It is therefore surprisingthat bars according to the invention give at least comparable after-washfeel properties to bars containing quaternary ammonium compounds nothaving polyethyleneoxide groups. This is particularly important sincepolyethyleneoxide quaternary ammonium compounds are potentially cheaperthan quaternary ammonium compounds not containing polyethyleneoxidegroups.

It will be appreciated that if a polyethyleneoxide quaternary ammoniumcompound showing little or no detersive activity is used in a baraccording to the invention a detergent compound or compounds must alsobe included in the bar. Detergent compounds can also be used, ifdesired, with polyethyleneoxide quaternary ammonium compounds that aredetersive. Suitable detergent compounds for such use include otherquaternary ammonium compounds, either containing a polyethyleneoxidegroup or not, zwitterionic compounds, amphoteric compounds, anioniccompounds and nonionic compounds.

It has surprisingly been found that some bars according to the inventiondisplay a number of other effects related to after-wash feel. These aremildness to the skin, moisturisation of the skin and protection of theskin against insult by anionic detergents.

Thus some polyethyleneoxide quaternary ammonium compounds have beenfound to be surprisingly mild to the skin. For instance, as shown inExample 203 hereinafter, certain polyethyleneoxide quaternary ammoniumcompounds are milder than related compounds not containing apolyethyleneoxide group. Thus, for example, compounds of the generalformulae 12.13. (cnmxand 11.15. (cnmcm. C5H5.X',

where R is a C to C straight-chain alkyl group or a C to Cstraight-chain alkyl group interrupted by a phenylene group, and X- is ahalide ion, have been found to be less mild than the same compoundswhere one or two methyl groups have been replaced by polyethyleneoxidegroups.

Therefore, in a preferred toilet bar according to the invention thepolyethyleneoxide quaternary ammonium compound has the formula where Ris a C to C straight-chain alkyl group or a C to C straight-chain alkylgroup interrupted by a phenylene group; R is a methyl or benzyl groupand R is methyl or (EO),,, and n is at least 3.

Detergent compositions are often expected to clean heavily-soiledclothes or dishes, often in very mild conditions, for instance at lowtemperatures and concentrations. Often compositions formulated toperform well in such conditions can be too powerful undiluted to beallowed to come into contact with sensitive skin without causingunpleasant, if minor, effects. Nevertheless, such contact, particularlywith dishwashing liquids, can occur in practice. It has been found thatuse of some bars according to the invention surprisingly mitigates theeffects of contact with such compositions.

The presence of polyethyleneoxide groups is believed to reduce thegermicidal activity of quaternary ammonium compounds, which compounds ingeneral contain at least one C to C straight-chain alkyl group. However,it has been found that if the polyethyleneoxide quaternary ammoniumcompound does not contain more than 40 ethyleneoxide units perquaternary nitrogen atom the compound has adequate germicidal activity,provided that the analogous compound without polyethyleneoxide groups,i.e. with such groups replaced by methyl groups, has germicidalactivity. A toilet bar with effective germicidal properties is obtainedparticularly if the bar contains a major proportion, that is more than50% by weight, of such a polyethyleneoxide quaternary ammonium compound.

It should be noted that the present invention is applicable to alltoilet bars comprising at least 15% by weight of a polyethyleneoxidequaternary ammonium compound as herein defined, which gives surprisingimproved afterwash feel and related effects. Nevertheless, the inventionhas two principal aspects, namely, a toilet bar comprising a majorproportion of a polyethyleneoxide quaternary ammonium compound on whichit depends for its detersive properties, and a toilet bar based on ananionic detergent compound and containing from 15 to 35%, preferablyfrom 20 to 30% by weight, of a polyethyleneoxide quaternary ammoniumcompound.

It is a particularly significant feature of the invention that it hasbeen found that polyethyleneoxide quaternary ammonium compounds aresurprisingly compatible with anionic detergent compounds. Quaternaryammonium compounds often form complexes with anionic detergentcompounds, which complexes often separate out with consequent loss ofdetergent action. It has been found that polyethyleneoxide quaternaryammonium compounds are surprisingly less likely to form complexes thatseparate out than are other quaternary ammonium compounds.

Also it has surprisingly been found that bars according to the inventionbased on anionic detergent compounds give a better after-wash feel thando bars based on anionic 5 detergent compounds containing analogousquaternary ammonium compounds.

Thus, a particular aspect of the invention isa toilet'bar based on ananionic detergent compound and containing from 15 to 35%, preferablyfrom 20 to-30%, by weight of a polyethyleneoxide quaternary ammoniumcompound.

It has further been found'that polyethyleneoxide quaternary ammoniumcompounds are surprisinglygood at dispersing lime. soap, that is theinsoluble soa-p normally formed as a scum when soap-bars are used inhard water. A particular feature of the inventionis therefore a toiletbar based onsoap, usually a sodium soap of C to C fatty acids, andcontaining from 15 to 35%, preferably from-20 to 30%, by'weight ofapolyethyleneoxidequaternary ammonium compound.

The preparation of toilet bars'based on an anionic nonionic orzwitterionic detergent compound and containing from 15 to 35% byweight'ofa polyethyleneoxide quaternary ammonium compound is achieved bythe standard techniques normally used for formulating bars based onanionic, nonionic or zwitterionic detergent compounds. In general, theseinvolve either casting, pressure moulding or plodding and stamping.However, with the inclusion of the polyethylene oxide quaternaryammonium compounds in the bars according to the present invention, itmay be necessary to adapt the compositions by, for example,incorporating' therein plasticisers, latherimprovers and hardeningagents, etc.

The formulation of bars. with adequate physico-chemical properties froma polyethyleneoxide quaternary ammonium compound alone or' in admixturewith a major or minor proportion ofother quaternary ammonium compoundsdepends on the particular compounds involved. But in general theproperties of quaternary ammonium compounds are such that bars canbemade by melting and setting the components. Again, plasticisers,lather improvers and hardening agents, for example, may be incorporatedin the bars, as described-below;

Generally the bars will include a hardening agent, but occasionally apolyethyleneoxide quaternary ammonium compound will require the use of asoftening agent. Compounds that are useful as softening agents includeamine oxides and-sulphobetai'nes; both also lather improversand C -Calkyl trimethylammonium quaternary ammonium compounds; Examples ofpolyethyleneoxide quaternary ammonium compounds that are so hard thatbars contain.- ing them generally need to besoftened are:

z )n where R is isopropyl', R is stearyl and m+n='50;- and polyethyleneglycol (M. Wt. 1000):

Often when one component, for example a polyethyleneoxide quarternaryammonium compound,.. has a low melting point and tends to make a bar toosoft, its effect can be counterbalanced by the use of another componentwhose hardening effect would otherwise. be normally too great. Examplesof polyethyleneoxide quaternary ammonium compounds that are very softare the compounds described in Examples 23', 3'0; 38', 41, 4'2, 43, 47,49, 50, 51-, 55, 6-1, 6-2, 63, 64 and 65 hereinafter, and- CxzHza E);

Ethoquad* 0 25 o1- orn (no it +r= and o n no 15 37 x: Ethoquad* 18/25 N01- on, E o). x y= 5 *Trademark, materials obtained from Armour HessChemi "C0;

The mechanism of action of hardening agents is not clearly understood.But it' is believed that most compounds are effective either becausethey are hard themselves or because they forma hard complex withpolyethylene oxide quaternary ammonium compounds.

Examples of classes of compounds that are. hardening agents because theyare hard themselves/include talc and polymeric materials, such aspolyvinyl alcohol, in powder form. Examples of classes of compounds thatare hardening agents because they apparently'f'orm a hard complex withat leastsome po'lyethyl'eneoxide quaternary am monium compounds includealkali metal salts of C to C alkane sulphonic acids, C to C fatty acidsand the alkali metal salts thereof, C 10 C alkyl succinic acids, C to Calkenylsuccinic acids and C to C alkane-Zl,3; 3-tricarboxylic acids.

It has been found that when a bar according to the invention contains ahardening agent the agent should preferablyconstitute from 2 to. 20%,particularly-preferably from 5Ito 15%, by weight-of thebar.

A number of classes of compounds are particularly and surprisinglyefliective hardening agents. "Such classes are as follows.

(A) Quarternary ammonium compounds not containing a polyethyleneoxidegroup andwhich contain at least one alkyl group. containing from L2. to.22 carbon atoms .in a straight chain, Preferred. compounds have thegeneral formulae:

where R and at least one of R1 and R are alkyl groups containing from12'. to 22 carbon atoms in a straightchain, any group R or R not beingsucharr alkyl group being an alkyl group containing from -1 to. 12carbon atoms, and X- is a compatible anion as discussed above:

(B) Carboxylic acids containing from 1 2 to 22. carbon atoms in astraight chain. This is surprising since. such fatty acids are softeningagents when used in toilet bars based on soap;

(C) Ethyleneoxide condensates of alcohols containing from 12' to 20carbon atoms in a straight chain, which contain from 20 ,to40-et-hyleneoxide units per molecule;

(D) Polyethylene glycols with molecular weights from 1,000 to 6,000; and

(E) Alkyl or alkenyl succinic acids in which the alkyl or alkenyl groupcontains from 10 to 18 carbon atoms in a straight-chain.

An important feature of a toilet bar is the lather obtained. in use. Theamount of lather produced by use of a bar varies considerably with thenature of the polyethyl eneoxide quaternary ammonium compound used. Asdiscussed below, lather fromua barcan" be improved, but a feature of theinvention is the surprising discovery that for polyethyleneoxidequaternary ammonium compounds. having a halide. anion adequate lather isgenerally obtained if the value of K is from 0 to 16, K being defined bythe expression:

where, 2 C is thesum of the carbon atoms contained in linear alkylchains containing more than 6 carbon atoms, 2 (E0) is the total numberof ethyleneoxide units and is the number of quaternary nitrogen atomspresent.

This is not an invariable relationship but is a useful guide to theprobable lathering characteristics of the polyethylene oxide quaternaryammonium compounds.

It is interesting that the condition is generally applicable tocompounds containing, for instance, aryl, amide or The C straight-chaincarboxylic acid is particularly useful since it acts both as a hardeningagent and as a lather improver.

It has further been found that a toilet bar according to the inventionlathers particularly well when the bar conester groups; that is,hydrophobic groups other than alkyl tains from 2 to 5% by weight of analkaline earth metal chains containing more than 6 carbon atoms, andhydrosalt of a C to C carboxylic acid, and the salt also acts philicgroups other than polyethyleneoxide groups do not a a hardening agent,materially affect the condition. Examples of polyethyleneoxidequaternary ammonium AS mentioned above, lather imPI'OVCTS can be Used incompounds for use in bars according to the invention and bars accordingto the invention. One featur 0f th i of their preparation are givenbelow. Most methods of vention is a toilet bar containing a polye hylenexi preparation give polyethyleneoxide quaternary ammonium quaternaryammonium compound and a lather improver. compounds not of 100% purity.The presence of minor Alatherimprover can act to increase the amount oflather mo nts of impurities does not substantially affect the a barproduces, to increase the quality, for example the essential propertiesof the compounds and their usefulcreaminess, of the lather, or toprovide lather when the ne in toilet b according t th in ention, barotherwise would lather to a negligible extent. In all of the Examplesparts and percentages are by It has been found that when a bar accordingto the inweight except where other ise indicated, vention contains alather improver this should prefer- Th preparation f o l compounds f thgeneral fo ably constitute from 2 to particularly preferably 20 mnla;from S to 15%, by weight of the bar.

Table I lists classes of compounds that can be used as R[CH;-CHOH-CHNIhR Rfl LX I lathe! improve in bars according to the mventlon' where Ris a mono-, dior tri-valent ethoxylated linking TABLE I group, R R and Rare compatible quaternary nitrogen substituent groups, n is from 1 to 3and X is a compati- (1) alkali metal Salts of c8 to C12 fatty acids; bleanion, are illustrated in Examples 1 to 32. Compounds (2) alkah Salts ofc8 to C12 alkyl .Sulphates; of this type in which R is a monovalent C Calkyl ether (3) ethanolamides of C to C fatty acids; group are shown inExamples 1 to 5. (4) ethylene oxide condensates of ethanolamides of C toc fatty acids (up to 25 E0 content); Example 1 (5) ta- 18 alcoholethoxylates (from 3 E0 to 20 E0 for 92.5 g. of epichlorhydrin was addeddropwise to 874 a- 12, and from 5 E0 to 25 E0 for 13- 18 alkyl g. oftallow alcohol14 EO containing 2 ml. boron trip fluoride etherate over15 mins. at 9095 C., and the mix- (6) alkali metalhydroxyalkylmethyltaurides, of the genture was Stirred for one hour. 10of alumina (1O0 eral formula 200 mesh) was added, the mixture stirredfor 15 mins.

R CH(OH)'CH2 N(CH3) CH2 CHZ SO3M and the alumina filtered off. Theproduct was tallow alh r 1where R is a C1 to C15 alkyl group and M 1s anal- 21 gfiig ggig g% gg all metal catlon, (7) sulphobetaines of thegeneral formula CH .CH(OH).CH CI,

prepared as above, and 168 g. of dimethyloctadecylamine were refluxed in200 ml. of n-butanol for 21 hrs. The n- Where R is a 12 to C18 alkylgroup; butanol was removed and the reaction product dissolved alkalimetal 1 to a alkylbenzene sulPhonatesi in 95% aqueous methanol, adjustedto pH 9 and extracted (9) a to 12 fatty acids; four times with 4060petroleum ether. The solid ob- Q; to m alkyldimethylamlne tained afterthe aqueous methanol had been removed con- (11) C to C alkylbenzenesulphonamldes; mined 89% of tallow alcohol fi E0 (12)polyethyleneglycols (M. Wt. 600 to 1500); (13) quaternary ammoniumcompounds not containing a polyethyleneoxide group, e.g. of the generalformulae: CH"CHwH)'CHNwHDZCBHWCh n-z rton) CH 0 H where R is o to 01'the K value 9f which is and H 2 5 a 8 Table II gives a 11st of examplesof compounds 51ml.-

larly prepared by the reaction of tallow alcohol-14 EO Rqfucnm where Ris on to C18 CH .CH(OH).CH Cl with various tertiary amines.

TABLE II Percent Wt. Reflux fin ii lifi Wt. (g.) tallow alcohol-14tertiary time compound K Example EOCHzCH(OH)CH2Cl Tertiary 8.1111116amine Solvent hours in solid value 1 22 Y fi$nriaaaarififiH.'.Z ii ii 53323i 4 64 N N-dimethyl-p-dode yl- 25 89 0,33

enzylamine. 5 64 N,N- dioctadeeylmethyl- 43 n-Butanol 90 72 0.24

X Excess pyridine was present.

Example 6 The preferred lather improvers are the sulphobetaines (7), theamine oxides (10), particularly where R is a C to C alkyl group and thepolyethylene glycols (12).

It has also been found that C to C carboxylic acids are particularlyuseful as additives in bars according to the invention since they reducelather properties less than any other of the carboxylic acids that canbe used as hardening agents.

-E E O-GHr CH( DE) -CH N(CH ):-CHrCI-Ig-CHz-NH-CO- CuHagCl'. This isprepared in a similar manner to that exemplified in Example 1 exceptthat 64 g. of tallow alcohol T EO-CH .CH(OH).CH Cl is reacted at refluxfor 42 hrs.

ample 1, by reacting 1,000- g-. of polyethylene glycol (M. Wt. 1,000)with 18.5 g. of epichlohydrin in the presence-of 3 ml. of borontrifluoride etherate. The chlorhydrin product obtained is designated Ain Table IV. Gther compounds: containing a reactive hydrogen atom weresimilarly converted to their chlorhydrins designated 13 to L as set out,with'weights involved, in Table III below.

TABI'JE III Grams of active Grams of Chlorhydrogen epiehlorhydrin Activehydrogen compound compound hydrin Be Howmomonn (nu-wt. 20o 200 185 C'-HO(CH CH1O),,H (In. wt. 600) 400 123' 2D". HO(CHZCH OEH (rmwt. 1,500)300 74 E- C1 H35CO-O-5 E u 252 '46 Fun. C1 H35CO-N-(CH CH;;Q)z-3 E0, 20074 G C15H31012 E0 400 49 H- Polypropylene glycol '(m. Wt. 800)- 50 3O .J300 14 -I- CHa'N (GH:OH20.)324 EO-I- 211 37 'CnHasCQNH-OHzCHaO-25 E0.341 23' K'. Glycerol-12230 620 278 L :.-I C1sH310-25 E0 .l 300 '21Random secondary pentadecanol derivative.

Table gives Examples'7 to 32 made by reacting the chlorhydrins of TableIII with tertiaryamines in a similar manner to that given in Example I.

10 units in the range from about"4 to 50 E0 units areusef-ulparticularly in toilet bars according to the invention.

These compounds are novel and a further aspect of the present inventionistherefore. a compound of the general formula:

CH3. A.(CH,.CH,.0) ,.B,2X or $.02 o)m( JJH-oH1.0) (Eo)ni3t2X where A andB are quaternary ammonium groups, z is from E to- 3 1-, yis from 1- 8-'to-t); m or n is-atleast 3 and m+n=4 to 50, and X" is a compatibleanion.

Such compounds as well as being useful for formulation into a baraccording to the present invention are also useful as detergents and asantistatic agents for the textile and polymer industries.

Particular polyethyleneoxide quaternary ammonium compounds based onpolyethylene-glycolsthat show this advantage are compounds of. the.general formula:

n mnn i.ontomomiom.

o on,.o zon,o11 on .ontf mlngaamwhere R R and R are compatible:quaternary nitrogen substituent groups,.Z is Z3 tofiand X- is acompatible anion.

Related compounds exemplified hereinafter and having the generalformula:

0 O t t R RlRzN. CH 0 (CH CHgO)... .ongmzimni, 2X

where R R R 2' and X- have the same significance as above, are alsonovel and of particularinterest for use in bars accordingito the.invention.

Polyethyleneoxide quaternary ammonium compounds for use in barsaccording to the inventioncan also be prepared by ,so-calledrquaternisation of amine ethyleneoxide condensates. Example 33exemplifies sucha prepa- TABLE IV .Iercent quater- Grams Grams N0. ofnary. am-

ofof Time at quatermonium chlor- .tert. reflux nary cornhydrin TertiaryAmine amine hrs! groups pound K value 69 N,N-d.imethyl dodecylamine 3423 2' 84 0. 68 400 N,N.-'d.imethyl octadecylamine. 223 48 .2 93 0. '5050 N ,N -dimethy-p-dodecylbenzyl amine. 31 44 2 80 0. 48 291N,N-dioctadecyl.methylamine 321 144 2 75 0. 29 50 N,N d.idodecylmethylamine 50 144 2 85 '0. 41 50 N,N dirnethyl*3-octadecanoylaminopropylann'ne 44 2 83 0. 46 56 N,N-dimethyl-aminoethyloctadecanoate47 42 2 85 0. 44 50 N,N-dimethyl octadecylann'ne 89 24 2 80 0. 10 154-do 150 50 2 94 0.30 50 N,N-dioctadecyl1 nethy1 amin 102 80 2; 83 0. 18100 N,N'-di1n'ethyl octadeoyl'amine 54 64 2 90 O. 74 50N,N-dioctadecylmethyl=amine 43 120 2- 77 0; 42 70 N,N-didodeeylmethylamine 46 64 2 86 0. 61 48 N,N-dimethy1 0'ctadeey1 amine 42 48 1'75 0. 12 48 N=hydroxyethylpolyethylene imine (m. wt..otipolyethyl- .1264 l 76 0.20

ene imine 600).

N ,N-dimethyl octadeoylanu'ne. 59 64 2 81 0.- 04 84 N;N dimethyloctadecylamine. 42 64 1 89 0. 32 84 N,N-dioctadeeylmethyl amine- 64 96 178 0. 22 104 N,N-dimethyl oetadecylamine. 21 64 2 75 0. 36 84 N,N-dioetadecyl methylamine- 32 967 2 81 0. 29 70 -N,N-di'methy1octadeoylamine- 51 64 4 77 0. 10 do i. 45 64 1 62 0.58 64 44 3 78 0. 0664 24 3 "-76 0; 07 75 48- 1 84 O. 61 15 I2 2 75 1. 64

Eer'monomer unit-a Polyethyleneoxide quaternary ammonium: compoundsration and Table V lists further Examples 34 to 60 made derived frompolyethylene glycols -(-m-. wt; from 200 to by analogous routes. 1500;i:e; about 475' to 3? E0) have been found to provide EMMPLEsurprisingly" good aft'efiwash feel when used, at levels v V V p v to ofit on Soap; Sodlum salts of stralghtcham C12 to C22 and heated at 6070'CL forZO hrs. The pH of the solufattyacidst v u r H r v H a tion waskept above pH 8 by the addltlon of SOdlllm The related compounds madefrom ethoxylated poly carbonate solution. The water and isopropanol wererep p y about 1000 3500 abeut' T8 t0 moved. Excess benzyl bromide wasremoved by washing propyleneglycol-nnits) with a greater number of E0 '5with 6080 petroleum ether. Inorganic salts were sepa- -In allcasesexeept Example 32 the solvent-used was n-but'anol; inExample 32 thesolvent was 2-methoxyethanoll.

where R 'is a compatible quaternary nitrogen substituent group, n is atleast 2, x is from 3 to 40 and X- is a compatible anion. In thepreferred compounds of this type where m+n=50 R is a C -C alkyl group orthe group:

where R is a C -C alkyl group and y is from 3 to 40.

TABLE V Percent quaternary am- Grams Grams monium of Quaternising ofTemp., Time com- Example Ethoxylated amine amine agent agent Solvent 0.hrs. pound value 34 Stearylamine-50 EO-- 5O Methyl iodine 5 None Reflux5 95 2. 63

35 "do 69 Isopropyl iodine Reflux 22 78 2. 38

36 .do 65 n-butyl iodine. Reflux 22 94 2. 2e

37 Stearylamine-40 E 70 p-lfideeiyl benzyl 48 90 1. 03

c on e.

38 4- alkyl amine-48 E0" 90 Methyl iodide 5 99 1.162-octadecamidoethylamine-1O EO 60 do 2A 80 0.48N-octadeeyl-n-propylenediamine- EO- 27 Octagecyl bro- 48 3 61 0.13

nu e. 41 do 76 Benzyl chloride.-- 24 3 73 0.21 Soya-amine5 E0 24 90 0.20Stearylamine-5 E0 24 93 0. Triethanolamine distearate 20 E0 24 78 0. 47Triethanolamine distearate-4 E0 45 Methyl chloride- 48 70 O. 12Triethanolamine distearate20 E 0 4 148 Benzyl chloride 48 78 O. 47Triethanolamine monostearate-EQ E0 56 Benzyl bromide-.. 24 80 1. 07Triethanolamine monostearate-IO E0 100 Methyl iodide 5 83 0. 48Triethanolamil1e 6 E0 50 Benzyl bromide 24 96 1. 29 Triethanolamine;24E0. 52 -...d0 24 93 3. 86 51 Didodecylamine5 E0 50 Benzy1ehloride. 48 940.16

52 DistearyIamine iEEO 50 Belfzyl bromide 48 70 0. 2s 53 Stearylamine-50E0 148 Hexaidecyl bro- 74 73 1. 47

54 Morpholine-Ti E0 162 Ofigeeyl bro- 6 94 0. e4

55 Dodecyl benzylamine-43 E0 50 Methyl iodide 24 70 2.15

56 -do 50 Dodccyl benzyl 24 95 1.13

chloride.

57 Polyethylene imine (in. wt. 600)4 EO. 22 Hexaleeyl bro- 72 82 0. 22

58 N-octadecyl-n-tripropylene tetra-amine-ll 50 Benzyl chloride... 24 800. 05

E0. 59 Triethanolamine-2 4 E0 50 Methyl iodide 24 98 27 60Trlethanolamine-24 E0 50 Ethyl iodide 24 90 13.5

Isopropanol. CHz-CHz-O-CO-CuHaa 2 Random primary amine.

9 It was found that for a substantial proportion of the product only oneN atom was quaternised; the percent quaternary ammonium compoundproduced was calculated on the basis of diquatermsation.

4 See the following formula:

The polyethylene oxide quaternary ammonium compounds prepared fromtriethanolamine are particularly interesting compounds for use accordingto this invention as they have humectant properties. These compounds arenovel and have the general formula:

NCHrCHn-O-CO-Ci1 as CHrCHg-OQO E0 7 Examples 44 and 46 made from thistriethanolamine di-stearate-20 E0 are the same compounds, but made underdifierent conditions of reaction. 5 Dimethylformamide.

Polyethyleneoxide quaternary ammonium compounds for use in barsaccording to the invention can also be prepared by the ethoxylation oftertiary amines with catalysts as shown in Example 61.

EXAMPLE 61 N,N dimethyl-Nfi EO- p-dodecylbenzylammonium chloride wasprepared as follows. Ethylene oxide was passed through 50 g. ofisopropanol at l20 C. containing 50 g. ofN,N-dimethyl-p-dodecylbenzylamine and 12.15 g. of 35% aq. w./w. hydrogenchloride until the required increase in weight had occurred. The productobtained after removal of solvent contained 96% of the requiredquaternary ammonium compound, which had a K value of 1.71.

Examples 62 to 65 in Table VI below illustrate the preparation ofrelated compounds from N,N-dimethyloctadecylamine and using a range ofacid catalysts.

TABLE VI Moles E0 in Amount used product Example Catalyst 13 2121 Thepolyethylene-oxide quaternary ammonium com- "l A BIiE vlI Continudpounds of Examples 63 to 65 have anions-other than the TestNo.Quaternary ammonium compound SDVI usual halide anions. However, itshould be noted that in x these and all other quaternary:-ammoniumcompounds 12 e whereRls the anions can'readily 'be changed ifdesiredbyconven- N 01- tionaLanion exchange techniques, either toichangeone cumcflz halide for another, 'or to substitute a halide for anon- Z 'halideanionor .vice versa. 13 139 Polyethyleneoxide quaternaryammonium-compounds N can be prepared'by'methods'other than thosedescribed F above. The following reaction routes are examples of the 1 4CH h many other reaction routes that are possible: +7 3 -w eres n as130 1. .-N po .b H R-(E0)n+'NCCHiOH "R(EO)nCHgGHzCN M .RIX =1mnonomomonmnz R(EO).,CHzCH;CH;1 IR X- 5 flwHav 125 \where.R. is theresidue of arcompound having a reactive vhydrogen before ethoxylation, n.is an integer of at least 1 CH3 3, R is analk-ylor-zalkaryl group and Xis a halide anion.

This reaction'is 'descr'ibed'in Schick, Nonionic Surfac- HawherecRlss'm' {150+ (tants, Vol. 1,'p. 1391 -(Edward ArnoldPublishers.Ltd., H-/ 1967). 2. ions ion;

q; 117- .ntotoo-NH-wnm \whoro'nisonnn 14o C1 iR-(EO) CH .CH(OH).CHn.NRa.X where R is the residue of a compound having a reactive CH3lhydrogenbefore ethoxylation, R is analkyl'groupand I 13R.0.C0-NH-(CHz)a whereRlsCfiH 26 n and X- are the same as above. 3

EXAMPLE66 Theability"of'polyethyleneoxide quaternaryam'monium CH3compounds to disperse lime soap scum was tested as 19 CH3 110 ip-onnqaotnl-cut A series ofaqueoussolutrons conta1n1ng 0.02, 0.05,.0.11, r 0.2, 05, 1'.0,'2'.0"and 550 'g.'/l. of each compound to betested were prepared using .deionised water.

A solutionof 0.25 ,g. of sodium oleate in 50 cc. of a a deionised Waterwas prepared. 5 cc. of the sodium oleate 40 EXAMPLE 67 solutiontogether'with 'IO'cc. of "hardwater (l 'litre'co'n- The'compafibflitywithianionicqdetergems ofi some tamed '9 and30-3 ethylene "oxidequaternary ammonium compounds acwere g i P 'Ngssler tubes one tube Qcording to the invention and some other quaternary am as a I antlishtube was addec1lJ 2Q 0 9 q l f' monium compounds 'wastes'ted asfollowsz wfater. FtZac i) t e refmilmng tu esdwas add d 2 10ml.'-of-a-2-%-aqueoussolution of the quaternary am- 0 linens O t b tha tFmonium. compound wastmixe d with 10 ml of a 2% aqueo e ess at u es e pace a a a -ous solution of the anionic detergent and the cloudiness .50C. for-one 'hour. The h ghest concentration of com- I t a hofthermixturegraded. pound WhlCh gave a clear solution to the eye wasnoted. clear 1 v The scum-d1spers1on1ndex (SDI) isdefinedasaperr 2-Centageequaltoslightlytcloudy fWt.compoundtogivemlear:solutioniinathistest Cloudy 4 Wt. oleate in thistest y c dy l y Table VILgives'results obtained with polyethyleneoxideThe results obtamed are gwen m Table VIII quaternary ammonium compoundsfor use in bars according to the invention and with other quaternaryammonium TABLE VIII 7 compounds. t Anionic detergent 1 6 I1 0 TABLE VIITest No. $313513? mm mm A n .0 9D est No. Quaternaryammoniumcompound SDI\1 5 7 CH3 5 5 5 5 1 Example 1 10 "Gr %xamp}e 3.- :g X810 8 a. t

4 .nnm1o 2L 66 CH3 5 Example 23. 2 5 '3" fi i i "2 "Cr u on; "5 "5 5 *5X 8 g J 5 8 Examgle 57 2 l-./ 9 N, N, N-trimethylhexadeeylammonium-bromide 128 /'N\ F01" 10 vR\+/OH;1 Where-"R is 051111 150+ CH3CHzChH r 4 -CBH6OH2 CH3 w 4 11 'R CH3 where R is CioHn 150 N 01 \iii/ o1CH3 j (CH'zYs'N'H GO "GnHas canon, \CH3 See footnotes at end of table.

Quaternary ammonium Anionic detergent 1 Test No compound A B C D 4 CisHm(130); 1 1 2 2 5 CH; (130)., m+n=l5 v 1 A=Sodium lauryl sulphate; B=Sodium dodecylbenzene sulphonate;

C=CnH3yCOO-CH;CHSO3NA; D =S0dium oleate.

Commercially available from Armour Hess Chemical Company under the tradename Ethoquad 18/25.

The polyethylene oxide quaternary ammonium com- .15 pounds givethebetter results.

All the polyethylene oxide quaternary ammonium compounds illustrated inExamples 1 to 65 can be formed into bars according to the invention.

Examples of particularly good bars according to the -2( invention whichincorporate major proportions of polyethylene oxide quaternary ammoniumcompounds are set out in Table IX below. All of the bars Were made bymelting the components together and pouring the melts into moulds madefrom aluminium foil. All melts set to solid bars within 24 hours, m'ostwithin 2 hours.

TABLE IX Polyethylene oxide quaternary ammonium Per- Per- Ex.comp0und(s) cent Other c0mponent(s) cent 68 Example 8-... 90 Coconutethanolamide 10 e9 ..do so do 10 N ,N-dimethyl-N-benzyl- 10noctylammonium chloride.

70 .--do 30 Sulpllobetaihe 10 Stearic acid 10 71 ..d0 8O Coconutethanolamide 10 N,N-dimethyl-N-benzyl-n- 10 octylammonium chloride.

72 -.d0 75 ...do 10 Stearic acid..-- 10 Calcium stearate... 5

73-... ..d0 65 N,N-dimethyl-N-benzyl-n- 10 octylammonium chloride.Stearie acid 10 Amine oxide 10 Calcium stearate... 5

74 ..(10---'---..- 75 Amine oxide 10 Stearic acid.-. 10 Calcium stearate5 75 .;.d0 75 Sulphobetaine 10 Stearlc acid 10 Calcium stearate 5Example 1....

77 Example 8-.-- 80 Amine oxide 74 10 Tallow fatty acid 10 78--d0---..---- 80 Amine oxide 3 10 Palmitic acid 10 '79 "d0 80 Amineoxide 10 Myristic acid 10 6O 8O d0 80 Amine oxide 10 Laurie acid 10 81"d0 40 Palmitic acid 10 Example 1.--. 40 Amine oxide 1 10 82Example.8-... Calcium stearate 5 83 ..do 75 Amine oxide 1 Laurie acid 10r Calcium stearate g 84..-:. Example 12..- 9o Amine oxide 10 85 .;.-.do90 Sulphobetaine 10 86 Example 8....;; 75 Amineoxide 10 Tallow fattyacid; 10 Calcium stearate 5,75

TABLE IXContinued Polyethylene oxide quaternary ammonium Per- Per- Ex.compound(s) cent Other component(s) cent 87 d0 70 Sulphobetaine 10 N,N-dimethyl-N-bcnzyl-n- 10 octylammonium chloride. Stearic acid 10 88..d0 80 Amine oxide 2 10 Amide quaternary 10 compound.

89 d0 7O Amine oxide 7 10 Amide quaternary 10 compound Pallnitic acid 1090 do 60 Coconut ethanolamide 10 N,N-dimethyl-N-benzyl-n- 2Ooctylamrnonium chloride. Palmitic acid 10 91 do 80 Coconut ethanolamide10 N ,N -dimethyl-N ,N-stearyl 10 ammonium chloride.

9 ..d0 N,N-dimethyl-N-benzyl-n 20 octylammonium chloride. Coconutethanolarnide. 10 Palrnitic acid 10 Glycerol monosteara 5 93 ..doCoconut ethanolarnide 10 N ,N-dimethyl-N-benzyl 20 octylalnmoniumchloride. N ,N-dimethyl-N ,N-distearyl 10 ammonium chloride.

94 Example 12--- Coconut ethanolamide 20 Myristic acid 10 95 Example 8.45 Coconut ethanolamide 15 Example 10-.- 30 Myristic acid 10 96 Example8. 45 Sulphobetainc 15 Example 10.-. 30 Palmitic acid 10 97 Example1---- 90 Coconut ethanolamide 10 98 ..do so do 10 Stcaric acid 10 99 do80 Amine oxide 2 10 Tallow alcohol- E0 10 100 d0 9O Sulphobetaine 1 10101-.-. --d0 do. 10 Stearic acid. 5 Calcium steara e 5 10 do 80 Amideoxide 2 1O Stearic acid- 5 Calcium stearate 5 103 ..d0 80 Amide oxide 21O Stearic acid 5 Glycerol monosteara e 5 104 .-do 75 Tallow alcohol-i5E0 10 Amide oxide 10 Stearic acid 5 105 .do Amide oxide 2 5 Amidequaternary 1O compound.

106 --do 7o Tallow alcohol2 5 E0 10 Amide oxide 2 10 Palmitic acid 10107. Example 12. Coconut ethanolamide 20 Glycerol monostearate 1010s-.... Example 1.-.. 7o Tallow alcohol2 5 E0 10 Amine oxide 2 10Laurie acid 10 Example 5. 30 Example 3- 40 110.-.-- Example 1-.-. 50

Example 3. 50

111.-.-- Example 53-.- 100 Amine oxide 2 1O 90 Coconut ethanolamide 1090 Sulphobetaine 1 10 90 Polygghyleueglyeol (m. wt. 10

1, 80 N,N,N-trimethylhexadecy1 20 ammonium bromide.

117 ..do.-. 80 Amine oxide 2 10 Amide quaternary 10 compound. 3

TABLE IXContinued Polyethylene oxide quaternary ammonium Per- Per- Ex.compound(s) cent Other component(s) cent 118 do 80 Coconut ethanolamide10 ide quaternary 10 compound 119 .-do 70 Amide oxide 2 l Amidequaternary compound. 3 Stean'c acid 10 120 .do 60 Amide oxide 2 10 Amidequaternary compound. 3 Stearic acid 10 Glycerol monostearate 10 121 do80 Amine oxide 2 10 Palmitic acid 10 122. Example 15. 45 Coconutethanolamide Example 16--- 3O Myristie acid 10 123 .do 80 Amine oxide 210 Palmitic acid 10 124"--. Example 31--- 80 Amine oxide 2 10 Palmiticacid 10 125.- Example 17..- 100 126 do 8O Amine oxide 1O IaLmitic acid10 127. Example 34. 80 Amine oxide 2 10 Tetradecylsuceinic acid 10 128.Example 25. 80 Palmitic acid 129.. Example 29-.- 100 13o -do so Amineoxide 2 1o Palmitic acid 1 131. Example 22. 70 Coconut ethanolamide. 20Palmitic acid 10 132 Example 35.-- 80 Amine oxide 10 Tetradecylsucci 10133. Example 7...- 134 (the C E alkyl group is derived from coconutfatty acids.

3 See the following formula:

4 See the following formula:

Call -011w O Na) -CH( S OsNa) (CO Na) The following Examples in Table Xare of bars according to the invention based on various anionicdetergent active compounds with minor amounts of polyethylene oxidequaternary ammonium compounds.

TABLE X Polyethylene oxide quaternary Detergent ammonium Example base 1Percent compound Percent A Example 16 20 A 80 Example 17 20 A 80 Example28 20 A 80 Example 51 20 A 80 Example 22 20 A 80 Example 30 20 A 80Example 10 20 A 80 Example 8 20 B 80 Example 10- 20 B 80 Example 17 20 B80 Example 28- 20 B 80 Example 51 20 B 80 Example 22- 20 B 80 Example30- 20 B 80 Example 10. 20 B 80 Example 8...- 20 C 80 Example 16 20 C 80Example 17. 20 C 80 Example 51 20 C 80 Example 22--. 20 C 80 Example 30.20 C 80 Example 10- 20 C 80 Example 8 20 D 80 Example 16- 20 D 80Example 17 20 D 80 Example 28 20 D 80 Example 51 20 D 80 Example 22- 20D 80 Example 30. 20 D 80 Example 10- 20 D 80 Example 8 20 E 80 Example16- 20 i E 80 Example 17 20 E 80 Example 28 20 E 80 Example 51 20 E 80Example 22- 20 E 80 Example 30 20 E 80 Example 10. 20 E 80 Example 8 20F 80 Example 16- 20 F 80 Example 17- 20 F 80 Example 28 20 F 80 Example51 20 F 80 Example 22- 20 F 80 Example 30-.- 20 F 80 Example 10- 20 F 80Example 8. 20 G 80 Example 16- 20 G 80 Example 17 20 G 80 Example 28 20G 80 Example 51 20 G 80 Example 22- 20 G 80 Example 30- 20 G 80 Example10- 20 G 80 Example 8- 20 1 The detergent bases were as follows:

x%=%0/20 mix of sodium soaps of fatty acid derived from tallow and nu o1B =50/50 mix of sodium soaps of fatty acid derived from tallow and nutoil together with 10% by weight of the mix of free fatty acid derivedfrom the mix.

0:95/5 mix of sodium soaps of fatty acids derived from tallow and sodiumnonanol sulphate (nonanol is a commercially available mixture of Calcohols and consists of 3,5,5-tri-methyl hexanol together with minoramounts of other branched chain nonanols).

D=60% Commercial coconut oil Igepon A; 25% Sodium soap frclnn 8 2/23,tallow/nut oil; 5% Fatty acids derived from 80/20 tallow/nut oi 10 ater.

E=60% Sodium soaps from 80/20 tallow/nut oil; 6% Fatty acids from 80/20tallow/nut oil; 12.5% Sodium 12-15 alkyl sulphate; 12.5% Potassium 12-15alkyl sulphate; 9% Water.

F=60% Commercial coconut oil Igepon A; 10% Sodium soap from 80/20tallow/nut oil; 20% Stearic acid; 5% Coconut fatty acid; 5%

Water.

G=25% Sodium 0 alkane sulphonate; 25% Sodium C15-13 alkane sulphonate;50% Sodium C olefin sulphonate.

H=The toilet bars of Examples 189 to 196 which were based on mixtures ofalkali metal alkane sulphonates and olefin sulphonates had particularlygood lather properties. Suitable alternative mixtures of alkali metalalkane sulphonates and olefin sulphonates are described in our U.K.patent specification No. 1,171,616.

EXAMPLE 197 Bars made from the polyethyleneoxide quaternary ammoniumcompounds of Examples 1 to 65 and the bars of Examples 68 to 196 weretested for after-wash feel. A panel of skilled assessors was used. Theprocedure was as follows:

Each panel member washed his or her hands with a bar made from thedetergent base A in Table X, and rinsed them thoroughly. The hands werethen Washed with the experimental bar. At each washing the panel memberused his or her normal Washing technique. After washing with theexperimental bar and rinsing, the hands were dried with a hair-drier andthe hands rubbed together to assess the after-wash feel.

19 In all cases improved after-wash feel was obtained. Bars based onBases A and B in Table X and containing polyethyleneoxide quaternaryammonium compounds within the general formula:

where A and B are quaternary ammonium groups, z is T and 34, and X is acompatible anion,

gave particularly good after-wash feel.

EXAMPLE 198 Bars made from the polyethyleneoxide quaternary ammoniumcompounds of Examples 1 to 65 and the bars 111 00.NH.(CH1);I I(CHa); Thebars according to the invention all showed afterwash feel comparable to,or better than the bars containing quaternary ammonium compounds notcontaining a polyethyleneoxide group.

EXAMPLES 200 TO 202 Three further bars according to the invention weretested against bars made from the same bases but not containingpolyethyleneoxide quaternary ammonium compounds by the procedure ofExample 198. The formulations of the bars were as shown in Table XI:

Nona-In all cases improved after-wash feel was obtained.

of Examples 68 to 196 were also assessed for after-wash feel by a panelof skilled assessors as follows:

After each panel member had washed his or her hands in the detergentbase A in Table X, rinsed and dried them, the fingers and thumb of theleft hand were each dipped in different solutions for 5 seconds. (Eachsolution was a aqueous solution of a bar being tested and was incubatedat 40 C.) The fingers were then rinsed and dried with a hair-drier.After-wash feel was assessed by rubbing the fingers of the left handwith the corresponding fingers of the right hand.

Again in all cases improved after-wash feel was noted.

EXAMPIJE 199 The bars of Example 68 to 196 were also accessed in aseries of tests in comparison with bars made of the detergent Bases A toG of Table X and bars made of the same bases but containing of aquaternary ammonium compound not containing a polyethyleneoxide group.

The quaternary ammonium compounds not containing a polyethyleneoxidegroup used were:

EXAMPLE 203 of each solution was injected intradermally into 4 rabbits.

Each injection site was marked and observed after 24 and 48 hours whenmeasurement of the length and breadth of the reaction mark in mm. wasmade.

Comparison of up to 8 materials can be made on each rabbit. The mean ofthe length and breadth of each reaction mark on each rabbit wascalculated; then the mean result for the 4 rabbits.

Cetyl trimethylammonium bromide (CTAB) was used as a standard. Relativeirritancy was defined as:

Mean diameter of reaction mark with test compound at 0.5% concentration(24 hours) Mean diameter of reaction with CTAB at 0.5 concentration (24hours) (1) 0151131 CH3 Results are given in Table XII below whichincludes or some tests on quaternary ammonium compounds not containingpolyethylene oxide groups for comparative pur- CIBHW CH1 50 poses. Thestructures of the compounds are given in Table (2) XXII to show therelationship between the similar ethoxyl- 5050mlxt t1 CHNCH B- I and rated and non-ethoxylated compounds with quite different EHUKKCHQmCHgCaHsrelative irritancies.

TABLE XII Test Relative No. Compound irritancy 1 C12H25 CH3 0.82

C1- CH3 CH3 2 C12H25 E0): 0.61

I o1-x+ =i5 CH3 (E0) Prepared similarly to Example 34 from dodeeylamine-i5 E0 and methyl chloride.

3 CiaHau CH3 0.00

01- GHa CH3 4 C18Ha7 CH3 0.55

0H3 (EON) Prepared similarly to Example 62 by ethoxylating stearyldimethyl amine in the presence of HCl.

TABLE XII-Continued Test Relative No. Compound irritaney CiaHen (E 0) z0. 34

fi I 50 y: CH3 E0) As prepared in Example 34 N\ 01 0E3 CH3 CmHzs- OHa CH/N\ 01- CR! O)4u As prepared in Example 61 but ethoxylated to a higherdegree.

8 Cis s1 0.98

N Br'x+y=5 C 2 N As prepared similarly to Example 43 but using benzylbromide.

9 C1EH37 0.44

\ /N\ B1-x+y=50 As prepared in Example 33.

N Clx+y= C 2 w Prepared similary to Example 33 but using benzylchloride.

11 C11 a5COOCHzCH2 (E0); 0.18

\ /N\ Brx+y=32 As prepared in Example 46.

l+ 0.19 CH3(CHz)mC 0 O (EO) CH2-OH(OH) CH2NCH2-CH2 G1 HzCHzOH a Asprepared in Example 21.

(CHzCHzO) CH2CH(OH) OH -N-(CHQzCHgCHzO-C 0 01 113 01- z is about 21 asprepared in Example 13.

(CHgCHzO) z CH2CHOH-CH2N(CH3)2'013F137 2, C1-

2 is about 5, as prepared in Example 8.

These results show that compounds of the general formula:

Kimmie- 120pxwhere R is a C to C alkyl group; R is a methyl or benzylgroup; R is a methyl or (E0) group, n is at least 3 and X- is a halideion, are surprisingly mild, particularly in the case of compoundscontaining at least 20 (E0) units.

There is some indication from similar tests that solu-- bility, E0content and molecular Weight are significant. Thus, compounds of thegeneral formula:

The presence of higher fatty acyl groups (C -C in the polyethylene oxidequaternary ammonium compounds also appears to make the compoundsexceptionally mild, as illustrated by Tests 11, 12 and 13.

EXAMPLE 204 The polyethylene oxide quaternary ammonium compounds thatare listed in Examples 1 to 65 and that have a halide ion Were testedfor lather characteristics, both quantity and quality. The followingcompounds displayed adequate lather properties or better:

Examples 2, 3, 4, 7, 8, 9, 11, 12, 14, 15, 17, 18,19, 23,

25, 26, 27, 28, 29, 30, 31, 41, 42, 43, 57 and 58.

Of these only for Example 18 and 25 is the value of K defined by theexpression:

EXAMPLES 205-210 Bars were prepared with the formulations shown in TableXIII below:

TABLE XIII Polyethylene oxide quaternary am- Detergent monium Examplebase 1 Percent compound Percent 90 Example 8. 1O 90 Example 10. 10 90Example 30 10 90 Example 8. 10 90 Example 10 10 90 Example 30. 10

1 Detergent bases as used in Table X.

These bars were compared with the bars of Examples 147, 148, 149, 194,195 and 196 for after-wash feel by the procedure of Example 198.

Although the bars of Examples 205 to 210 showed some slight improvementin after-wash feel, the effect was very much slighter than that shown bythe bars of Examples 147, 148, 149, 194, 195 and 196.

EXAMPLE 21 1 The bar of Example 89 was tested against a conventionalsoap bar (50/50/10 tallow soap/nut oil soap/free fatty acids derivedfrom the tallow soap and nut oil soap) using a panel of 30 skilledassessors.

Each member washed his or her hands with the soap and then dried them.Then a laboratory technician washed one hand of the member with the soapbar and the other hand with the bar of Example 89. After both hands weredried the member assessed the after-wash feel of each hand, usually byrubbing the palm of the hand with the tips of the fingers of the otherhand.

In the experiment 24 members preferred the after-wash feel from the barof Example 89, 4 preferred that from the soap bar and 2 were undecided.

The procedure was repeated for the bar of Example 106 when excellentafter-wash feel results were again obtained, 21 of the assessorspreferring the bar containing the polyethyleneoxide compound to 4preferring the soap bar and 5 having no preference.

EXAMPLE 212 The skin moisturising effect of three polyethylene oxidequaternary ammonium compounds according to the invention was determinedby exposing portions of guinea pig foot-pad corneum to 20% w./w. aqueoussolutions of the compounds for 4 hours at room temperature. Each portionof treated corneum was then equilibrated in an atmosphere of 90%relative humidity (RH) and then weighed, after which it was transferredto a dry atmosphere and after a period of re-equilibration the sample ofcorneum was weighed again. The difference in weight is a measure of thewater-binding capacity of the corneum expressed as mg. of water boundper 100 mg. of dry corneum. A control experiment using distilled waterwas also conducted and the results are expressed in Table XIV below,each result being an average figure of at least 9 individual tests.

24 TABLE XIV Water Bound at RH Example No.: (mg/ mg. of corneum) 7 32.230 30.0 35 31.7 Control 22.7

These figures demonstrate a significant increase in the water-bindingcapacity of skin after treatment with aqueous solutions of thepolyethylene oxide quaternary ammonium compounds.

EXAMPLE 213 To determine the protective effect on human skin of washingwith aqueous solutions of polyethylene-oxide quaternary ammoniumcompounds, samples of human skin were treated by the following procedurein Table XV after being mounted in perspex cells over saline saturatedtissues.

TABLE XV Skin Sample Treatment A Exposed to a 1% aqueous solution of thepolyethylene oxide quaternary ammonium compound of Example 13 for 30minutes.

B Exposed to a 1% aqueous solution of the polyethylene oxide quaternaryammonium compound of Example 28 [or 30 minutes".

0 Exposed to a 1% aqueous solution of sodium lauryl sulphate for 30minutes".

D Exposed to a 5% aqueous solution of sodium lauryl sulphate for 30minutes.

E Exposed to distilled water only for 30 minutes.

F A small amount of the undiluted polyethylene oxide quaternary ammoniumcompound of Example 13 was rubbed into the skin using a Teflon rod for15 sec. and left in contact in the skin for 10 minutes; after rinsingwith distilled water for 2 minutes the skin was exposed to a 1% aqueoussolution of sodium lauryl sulphate for 30 minutes".

G The treatment was the same as for sample F except that a 5% aqueoussolution of sodium lauryl sulphate was used.

H The treatment was the same as for sample F except that thepolyethylene oxide quaternary ammonium compound was that of Example 28.I The treatment was the same as for sample H except that a 5% aqueoussolution of sodium lauryl sulphate was used.

The aqueous solution used was replaced with a fresh solution after 10minutes and again after 20 minutes.

After the initial treatment, each of the skin samples was rinsed inthree changes each of 2 minutes duration in distilled water and thenfixed in 5% aqueous solution of glutaraldehyde buffered to pH 6.9 withphosphate for 3 hours at 4 C. After fixation, the skin samples werethoroughly rinsed and then they were cooled rapidly in Freon 12 cooledto 158 C. by liquid nitrogen. The skin samples were then transferred toa Speedivac tissue drier and freeze dried overnight. The dry samples ofskin were then metal shadowed with gold/ palladium for examination in ascanning electron microscope.

Observation of each of the skin samples in the scanning electronmicroscope showed that pre-treatment of the skin with either of thepolyethylene oxide quaternary ammonium compounds according to theinvention before exposure to the solution of sodium lauryl sulphate wasbeneficial in that the degree of surface damage to the skin was markedlyreduced when compared with that obtained by treatment with solutions ofsodium lauryl sulphate alone.

EXAMPLE 214 A polyethylene oxide quaternary ammonium compound containingester linkages was prepared from polyethylene glycol as follows. 200 g.of polyethylene glycol (MW 1000) and 40 g. of chloracetic acid weredissolved in 300 ml. of toluene and refluxed for 24 hours. The waterformed during the reaction was removed by azeotropic distillation andthe solution allowed to stand over sodium carbonate 25 for one hour toremove chloracetic acid. The solution was filtered and the solventdistilled off to leave the compound:

I ll 01011.80 (CHzCHzO)nCCH2C1 where n is about 23 115 g. of thiscompound and 59' g. of N,N-dimethyl hexadecyl amine were refluxedtogether in 300 ml. of eth yl acetate for 24 hours. The ethyl acetatewas then removed and the reaction product was dissolved in 95% aqueousmethanol and extracted with 40-60 petroleum ether. The resulting solidcontained 72% of the compound:

where n is about The K value for this compound is 0.58.

A toilet bar was prepared from this polyethylene oxide quaternaryammonium compound and was found to have good lather and after-wash feelproperties.

What is claimed is:

1. A toilet bar containing from 15 percent to 100 percent by weight of apolyethylene oxide quaternary ammonium compound or compounds containinga polyethylene oxide group with at least three ethyleneoxide units in achain, which polyethyleneoxide quaternary ammonium compound is selectedfrom the group consisting of detersive polyethyleneoxide quaternaryammonium compounds having K values of from 3 to 0.01 and non-detersivepolyethyleneoxide quaternary ammonium compounds having K values of from30 to 0.67, the K value being defined by the expression:

where 2(EO) is the total number of ethyleneoxide units, EC is the totalnumber of carbon atoms not in ethyleneoxide units and 2N+ is the totalnumber of quaternary nitrogen atoms per repeating unit of the compound,and up to 20 percent by weight of a hardening agent selected from thegroup consisting of compounds of the general formula:

. Where R is a C to C straight-chain alkyl group, R

is a methyl group or C to C straight-chain alkyl group and X- is acompatible anion, C to C straight-chain carboxylic acids, compounds ofthe general formula where R is a C to C straight-chain alkyl group and nis from 20 to 40, polyethylene glycols with a molecular weight from1,000 to 6,000 alkyl and alkenyl succinic acids of the general formula:

R.CH (COOH) .CH COOH where R is a C to C straight-chain alkyl or alkenylgroup; and up to 20 percent by weight of a lather improver selected fromthe group consisting of alkali metal salts of C to C fatty acids, alkalimetal salts of C to C alkyl sulphates, ethanolamides of C to C fattyacids, ethyleneoxide condensates of ethanolamides of C to C catty acidswith up to 25 E0 groups, C to C alcohol ethoxylates containing 3-20 EOgroups, C to C alcohol ethoxylates containing 5-25 EO groups, alkalimetal hydroxyalkylmethyl taurides of the general formula:

where R is a C to C alkyl group and M is an alkali metal cation,sulphobetaines of the general formula:

R-N (CH3) z-CHzCHzCHg S 0 where R is a C to C alkyl group, alkali metalC to C alkyl benzene sulphonates, C to C fatty acids, C to 26 C alkyldimethyl amine oxides, C to C alkyl benzene sulphonamides, quaternaryammonium compounds of the general formula:

B-Kuorrmommm where R is C to C and quaternary ammonium compounds of thegeneral formula:

where R is C to C and polyethylene glycols with a molecular weight from600 to 1,500; and up to percent by weight of an anionic detergent activecompound.

2. A bar as claimed in claim 1 in which the polyethyleneoxide quaternaryammonium compound has the general formula where R is a C to Cstraight-chain alkyl group or a C to C straight-chain alkyl groupinterrupted by a phenylene group, R is a methyl or benzyl group, R is amethyl or polyethyleneoxide group and n is at least 3.

3. A bar as claimed in claim 1 containing at least 50% by weight of apolyethyleneoxide quaternary ammonium compound which contains at leastone C to C straightchain alkyl group and which contains no more than 40ethyleneoxide units per quaternary nitrogen atom.

4. A bar as claimed in claim 1 containing from 2 to 20% by weight of ahardening agent.

5. A bar as claimed in claim 4 containing from 5 to 15% by weight of ahardening agent.

6. A bar as claimed in claim 1 containing from '2 to 20% by weight of alather improver.

7. A bar according to claim 16 containing from 5 to 15% by weight of alather improver.

8. A bar as claimed in claim 1 in which the lather improver is a Cstraight-chain carboxylic acid.

9. A bar as claimed in claim 1 containing from 2 to 5% by weight of analkaline earth metal salt of a C to C straight-chain carboxylic acid.

10. A bar as claimed in claim 1 comprising a major proportion of apolyethyleneoxide quaternary ammonium compound having detersiveproperties.

11. A bar as claimed in claim 1 based on an anionic detergent activecompound and containing from 15 to 35% by weight of a polyethyleneoxidequaternary ammonium compound.

12. A bar as claimed in claim 11 containing from 20 to 30% by weight ofa polyethyleneoxide quaternary ammonium compound.

13. A bar as claimed in claim 11 in which the anionic detergent activecompound is soap.

14. A bar as claimed in claim 11 in which the anionic detergent activecompound is a mixture of alkali metal alkane sulphonates and olefinsulphonates.

15. A bar according to claim 1 wherein the polyethyleneoxide quaternaryammonium compound contains a higher fatty acyl group.

16. A bar according to claim 1 wherein the polyethyleneoxide quaternaryammonium compound has the general formula:

where R R and R are compatible quaternary ammonium substituent groups, Xis a compatible anion and n is an integer of from 1 to 3, and, when n isl, R is selected from the group consisting of C C alkyl O-(EO); C Calkyl COO-(E0); and C C alkyl CONH-(EO) where x is from 3 to 40, when nis 2, R is CsC22 alkyl CO-N where x or y is at least 3 and x+y=4 to 40and when n is 3, R is selected from the group consisting of CHz-O-(EO);

HO(EO) H2O(E O) r and (E R'N(EO) where R is a compatible quaternaryammonium substituent group, and x, y or z is at least 3 and x+y+z= to40.

17. A bar according to claim 16 wherein the polyethyleneoxide quaternaryammonium compound has the general formula:

Cs-Czz CH .CHOH.CH NR R R X.-

where R R and R are compatible quaternary ammonium substituent groups, xis from 3 to 40, and X is a compatible anion.

18. A bar according to claim 1 wherein the polyethyleneoxide quaternaryammonium compound has the general formula:

+ A and B are quaternary ammonium groups, 2 is from 13 to 5, y is fromT8 to W, m or n is at least 3 and 111+): is from 4 to 50, and X is acompatible anion.

19. A bar as claimed in claim 18 wherein the polyethyleneoxidequaternary ammonium compound has the formula:

R R R N.CH .CH(OH).CH1.O(EO),CH2CH(OH).CH:NR RzRa, 2X- where R R and Rare compatible quaternary nitrogen substituent groups, z is from 4. 5 to34 and X is a compatible anion.

20. A bar according to claim 18 wherein the polyethyleneoxide quaternaryammonium compound has the formula:

0 R1RzR N.CHz( J.O.(OHzCHzOL. .CHz.NR R R ,2X-

where R R and R are compatible quaternary nitrogen substituent groups, 2is from 1:5 to 3 1 and X is a compatible anion.

21. A bar as claimed in claim 18 wherein the polyethyleneoxidequaternary ammonium compound has the formula:

where R R and R are compatible quaternary nitrogen substituent groups, yis from 18 to E55, m or n is at least 3 and mi-i-n is 4 to 50, and X- isa compatible anion.

22. A bar according to claim 1 wherein the polyethyleneoxide quaternaryammonium compound has the general formula:

where R is a compatible quaternary nitrogen substituent group, at is 1or from 3 to 40, x only being 1 whene R contains the group --(EO) wherey is from 3 to 40, n is at least 12 and X is a compatible anion.

25. A bar according to claim 24, wherein R is a C C alkyl group or thegroup:

R'COO(EO) CH CHOHCH- where R is a C C alkyl group and y is from 3 to 40.

References Cited UNITED STATES PATENTS 2/1961 Hewitt 2S2Dig. 16

3,224,976 12/1965 Farrar et al 252Dig. 16

3,312,627 4/1967 Hooker 252Dig. 16

FOREIGN PATENTS 1,027,898 4/1966 Great Britain 252-Dig. 16

1,084,134 9/1967 Great Britain 260-567.6

WILLIAM E. SCHULZ, Primary Examiner US. 01. X.R.

252-92, 134, Dig. 16

